Lanthanide oligomerization catalyst

ABSTRACT

A catalyst composition consisting essentially of: A. a lanthanide series metal compound, e.g., cerous acetylacetonate, B. a reducing agent, e.g., ethylaluminum sesquichloride, C. a non-protonic Lewis acid, e.g., ethylaluminum sesquichloride, and, as optional, preferred ingredients, D. a trihydrocarbylphosphine, e.g., triphenylphosphine, and E. an inert, organic solvent, e.g., chlorobenzene, is disclosed as being useful for catalyzing the polymerization of olefins or phenyl-substituted olefins to normally liquid polymers or oligomers, e.g., for catalyzing the dimerization of propylene.

United States Patent 91 Yoo et al.

[ 4] LANTHANIDE OLIGOMERIZATION "CATALYST [75] Inventors: Jin Sun Yoo; Robert Koncos, both of Riverdale, Ill.

[73] Assignee: Atlantic Richfield Company,

Philadelphia, Pa.

[22] Filed: Nov. 5, 1971 [21] Appl. No.: 196,238

Related US. Application Data [62] Division of Ser. No. 727,735, May 8, 1968, Pat. No.

[52] US. Cl. 252/429 B, 252/428, 252/431 C, 525/431 N, 252/431 P, 260/683.15 D [51] Int. Cl. C07c 3/10 [58] Field of Search 260/683.l5 D; 252/431 C, 252/431 P, 429 A, 429 B, 429 C, 428

[56] References Cited UNITED STATES PATENTS 2.953.531 9/1960 Anderson et a1. 252/42 9 A 3,179,647 4/1965 Mulley et al..... 252/429 A X 3,366,704 1/1968 Stapp 252/429 x [451 Apr. 9, 1974 3,384,678 5/1968 Stapp 260/683.15 D 3,554,924 1/1971 Kittleman et a]. 252/429 A 2,898,329 8/1959 Kittleson 252/429 B X 3,408,418 10/1968 lwamoto et a1. 252/429 B X Primary Examiner-Patrick P. Garvin Attorney, Agent, or Firm-Thomas .l. Clough 5 7] ABSTRACT agent, e.g.,

trihydrocarbylphosphine. e.g., triphenylphosphine, and

E. an inert, organic solvent, e.g., chlorobenzene. is disclosed as being useful for catalyzing the polymerization of olefins or phenyl-substituted olefins to normally liquid polymers or oligomers, e.g., for catalyzing the dimerization of propylene.

15 Claims, No Drawings ethylaluminum 1 LANTHANIDE OLIGOMERIZATION CATALYST This is a division, of application Ser. No. 727,735, filed May 8, '1968, now US. Pat. No. 3,641,188.

The present invention relates to a novel catalyst composition and to the use of such catalyst in the polymerization or oligomerizat'ion of olefins and phenylsubstituted olefins to low molecular weight polymers or. oligomers. More particularly, the invention relates to a lanthanide series metal-containing catalyst system, e.g;, cerium-containing especially useful in catalyzing the dimerization of propylene.

Numerous catalyst systems have been disclosed in the prior art as being suitable for the preparation of polymers of olefins such as alpha-mono-olefms and conjugated diolefins, particularly to form low molecular weight dimers, trimers, tetramers, etc. of such olefins. Normally gaseous olefins such as propylene have, for example, been effectively dimerized using these catalyst systems to produce hexene fractions of varying composition. The polymeric and oligomeric products produced in such reactions are often valuable in either the petrochemical field or the fuel' industry or both. One of the major fractions of dimeric propylenes, 2- methylpentenes, can be utilized, for instance, for the synthesis of isoprene. Another propylene dimerization product, 2,3-dimethylbutene, is useful as a feed for the production of 2,3-dimethylbutadien'e which in turn can be used in a multi-step synthesis of pyromellitic anhydride, or can be hydrogenated to yield 2,3- dimethylbutane, useful as an octane-enhancing ingredient in gasoline. The latter compound, for example, has the highest research octane number l03.5) of those paraft'ms having boiling points up tol40F.

It has now been found that a catalyst composition containing a metal of the lanthanide series is extremely active in catalyzing the polymerization or oligomerization of such olefins to normally liquid polymers or oligomers, e.g., dimers, trimers, tetramers, etc. The catalyst composition of the present invention comprises a combination of (A) a lanthanide series metal compound, (B) a reducing agent, (C) a non-protonic Lewis acid and, as an optional ingredient,'(D) a trihydrocarbylphosphine. As will be discussed hereinafter, ingredients (B) and (C) can both be supplied by a single component which performs both reducing agent and Lewis acid functions. Preferably, there will also be included in the catalyst composition an inert organic solvent in amounts up to about 99 percent, preferably about 80 or 90 to 95 percent, based on the combined weight of (A), (B), (C), (D) and said solvent, i.e. based on the weight of the total catalyst composition.

The lanthanide series metal compound, component A of the catalyst composition, may be supplied byvarious lanthanide series metal compounds, including lanthanide series metal salts of mineral acids, lanthanide series metal salts of carboxylic acids of at least 4 carbon atoms and lanthanide series metal complexes. As examples of suitable mineral acid salts may be mentioned the lanthanide series metal nitrates, cyanides, halides (especially the chlorides and bromides), etc. The carboxylic acids whose lanthanide series metal salts can be employed as component A in'the composition will generally have at least 4 carbon atoms and can have as high as about 30 or more carbon atoms. Included among the suitable acids are poly-, e.g. di-, carboxylic acids as well as monocarboxylic acids, and aromatic as well as aliphatic (including cycloaliphatic) carboxylic acids. Ethylenically-unsaturated as well as saturated carboxylic acid salts can be employed also. Thus there can be used, for example, salts of the following acids: phenylacetic, phenylpropionic, caproic, palmitic, stearic, vinylacetic, undecenoic, crotonic,-adipic, decanel, 10- dicarboxylic, muconic, cyclohexane carboxylic, cyclohexane dicarboxylic, benzoic, naphtonic, phthalic, isophthalic, terephthalic, dimethoxyacetic, dimethoxypropionic, dimethoxyacrylic, dimethoxymonochloroacetic, dimethoxybenzoic, dimethoxymalonic, dimethoxyadipic, etc. The hydrocarbon carboxylic acids are often preferred, and among the fatty acids those of 4 to 7 carbon atoms are often preferred.

It is frequently advantageous to employ as component A of the composition a lanthanide series metal complex, preferably one wherein the electron donor portion is a weak field ligand. The term complex" is here used synonymously with coordination compound and is intended to embrace complexes with monodentate complexing agents, i.e. those agents which contain onlyone electron donor group, as well as complexes with polydentate complexing agents, i.e. those agents, usually organic, which contain two or more electron donor groups. The latter complexes, known as chelates, are often preferred for use in the catalyst composition of the present invention. There may advantageously be employed those complexing agents wherein the electron donor atoms are selected from the nonmetallic elements of Groups VA and VIA of the Periodic Table, e.g., O, N, S and P. As suitable oxygencontaining complexing agents there may be mentioned, for instance, carbonyl, hydroxyl and carboxylate group containing compounds, and often preferred are, for example, the beta-diketones, the beta hydrOXyaIdehydes, the beta-ketocarboxylic acid esters, the dialkoxycarboxylic acid esters, etc. As suitable nitrogencontaining complexing agents may be mentioned, for instance, primary, secondary and tertiary amino group containing compounds as well as oximes, imines and imides. As examples of suitable sulfur-containing complexing agents there may be mentioned the thioalcohols, thioketones thioethers, etc. And as suitable phosphorus-containing complexing agents there may be mentioned, for instance, the phosphines. The oxygencontaining complexes are often preferred for use in the catalyst composition of the present invention, and as specific examples of such may be mentioned: acetylacetonates, propionylacetonates, benzoylacetonates, complexes with salicylaldehyde, etc.

Often preferred as the lanthanide series metal is cerium, which may be supplied either as a cerous or a ceric compound, for example as cerous acetylacetonate.

The reducing agent, component B, is supplied by a compound which is compatible with component C, the Lewis acid, and which is capable of reducing the lanthanide series metal in the lanthanide series metal compound, preferably to an oxidation state lower than 1 and even to zero. The reducing agent should not, however, be effective to reduce the metal to its elemental state.

The Lewis acid, component C, is supplied by a compound which is other than a protonic, or hydrogen, acid and which is capable of receiving one of more pairs of electrons to form a coordinate covalent bond. Lewis acids are well known to the art and are fully defined,

for example, by Nolher, .Chemistry of Organic Compounds, W. B. Sanders Company, 1951, at pages 233-235: by Stone, Chemical Review, vol. 58, 1958, at page 101: and by their namesake, G. N. Lewis, Journal of the Franklin Institute, 226, 293 (1938).

As mentioned above, both B and C may be supplied by a single compound which performs both functions. As examples of such a compound may be mentioned the acidic organometal halides which correspond to the general formula ta-u) v wherein M is a metallic element of coordination number n whose halides are Lewis acids, X is halogen having an atomic number of 9 to 53 (i.e., fluorine, chlorine, bromine or iodine), R is hydrocarbyl, e.g. alkyl,- of 2 to about 6 carbon atoms and y is a number having a slsqfw s ata. h fltqlsssfi an ilt ttqille ins a value from 1 to n- 1. Often preferred metallic elements in the abovecompound include aluminum, zinc -and tin. As examples of suitable such acidic organometal halides may be mentioned the alkylaluminum halides, including mono-, sesqui-and dihalides, and as specific examples of suitable alkylaluminum halides may be mentioned diethylaluminum chloride, iodide and bromide; ethyl aluminum dichloride, diiodide and dibromide; and ethylaluminum sesquichloride, sesquiiodide and sesquibromide.

When, however, the particular reducing agent employed in the composition does not also perform as a Lewis acid, it is necessary to separately supply the Lewis acid to the catalyst composition. Examples of reducing agents which are suitable as component B in the composition but which do not perform satisfactorily as Lewis acids therein include trialkylaluminums, monoalkoxydialkylaluminums, and dialkylaluminum hydrides wherein the alkyl and alkoxy groups contain up to about 6 carbon atoms: Grignard reagents: ally] and alkyl tin complexes; and compounds of the formula MAlR', and MBeR wherein M is an alkali metal, e.g., sodium, lithium or'potassium, and R is alkyl, for example of 2 to 6 carbon atoms.

- And, correspondingly, as examples of suitable Lewis I acids which do not perform as reducing agents in the system may be mentioned aluminum chloride, zinc chloride, stannic chloride, boron trifluoride, boron trifluoride etherates, e.g., the diethyl etherate, etc.

The trihydrocarbylphosphine component, optional ingredient (D) of the catalyst of the present invention, can be supplied by a compoundcorresponding to the general formula R wherein R is a hydrocarbon radical of l-to about 12 carbon atoms. Preferably, R is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl radicals and is devoid of olefinic or acetylenic unsaturation; different R's may, of course, be present in the same phosphine molecule. When the phosphine component contains aromatic groups it is generally preferred that these have mono-cyclic structures, i.e., that the groups be selected from phenyl, alkylphe'nyl, or phenylalkyl radicals.

The presence of the, phosphine component, which apparently can enter into a complex-forming reaction with the lanthanide series metal compound, makes for a more active catalyst composition. It is seen that the phosphine component is monodentate, or unidentate, i.e., unifunctional, as regards the phosphorus atom. Use of multifunctional phosphines such as bi s(diphenylphosphino)ethane inplace of the unidentate phosphine in the catalyst composition of the present invention has been found, for example, to result in a composition showing no catalytic activity for the dimerization of propylene. ,As examples of suitable phosphines, then, may be mentioned triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, tri-n-hexylphosphine, tri-n-decylphosphine, tribenzylphosphine, tri-(4-nbutylphenyl)phosphine, and the like.

The molar ratio of component B (reducing agent) to component A (lanthanide compound) in the catalyst composition is about 3 to 40:1, preferably about 5 to 30:1. (For reasons of economics, however, it may often be preferable to employ no more than about 15 moles of component B per mole of component A). Similarly,

the molar ratio of component C (Lewis acid) to component A (lanthanide compound) is also about 3 to 40:1, preferably about 5 to 30: 1. (Again, for economic reasons it may be preferable to employ no more than about 15 moles of component C per mole of component A).

Where optional component D (phosphine) is included in the composition it can generally be present in amounts up to about 10 moles or more per mole of component A, and will often be present in amounts of about 1 to 6 moles per mole of said component A. (Economic considerations, however, may. dictate that no more than about 4 or 5 moles of phosphine be employed per mole of component A).

The trihydrocarbylphosphine component, if employed, may advantageously be pre-admixed with the lanthanide series metal compound and the reducing agent and Lewis acid added to the resultant mixture. Depending upon the pre-admixing temperature and the particular lanthanide series metal compound and phosphine employed, it is believed that the lanthanide compound and the trihydrocarbylphosphine may react together, for instance in an approximately equimolar ratio, to form a complex. It is further thought that some of the phosphine, when brought into contact with the remaining components of the catalyst composition, i.e. Components B and C, might also enter into a complexforming reaction with those components as well. Accordingly, there may be present in the catalyst composition amounts of trihydrocarbylphosphine in excess of that, if any, which is complexed with the lanthanide seriesmetal compound. Where, for example, an acidic organometal halide or a trialkylaluminum is employed in the composition it is preferred that there be an excess of trihydrocarbylphosphine present, i.e. in addition to that which is complexed with the lanthanide series metal compound, this excess apparently complexing with a portion of the acidic organometal halide or trialkylaluminum to form a more active catalytic composition.

As indicated above, the preparation of the preferred catalyst composition, i.e. that wherein component D is included, is preferably conducted by first admixing the trihydrocarbylphosphine with the lanthanide series metal compound in the presence of a suitable organic solvent and then adding to the resultant solution or suspension the reducing agent (component B) and the Lewis acid (component C). The pre-admixing of components A and D may be conducted at room temperature or lower, or as high as about 300F. The use 'of elevated temperatures, say about F. or higher, and often from about 120 to 200F., is believed to be more conductive to the formation of a complex between the lanthanide compound and the phosphine compound than are room temperatures or lower. It is often desirable to waita short period of time after pre-admixing components A and D, say about 5 to 30 minutes, before adding components B and C to the pre-admixture.

Where component D is omitted from the catalyst composition, no advantage is known to reside in the use of any particular mixing sequence and the composition can be formulated by simply admixing components A, B and C, preferably in a suitable organic solvent.

Suitable solvents for the admixing procedures described above include the same solvents as those which are suitable for use in the final catalyst composition. If desired, however, where components A and D are preadmixed, such pre-admixing may be accomplished in a solvent which is unsuitable for use in the final catalyst composition; in this case the pre-admixing solvent should then be removed from the solution or suspension and the residue re-dissolved or re-suspended in a proper solvent which is inert to the final catalyst composition.

Suitable .organic solvents for the final catalyst composition are those which are inert to the catalyst and which will not enter into, or deleteriously affect, the eventual polymerization or oligomerization reaction. As specific examples thereof may be mentioned aromatic and aliphatic hydrocarbons and their halogenated, e.g. chlorinated, derivatives such as, for instance, chlorobenzene. Oxygen-containing solvents are generally to be avoided for'this purpose.

The combining of the catalyst components is preferably conducted in a dry, inert atmosphere, out of the presence of air, for instance in an autoclave. Within a relatively short period of time after the admixing of all the components, e.g. about 5 to minutes, an active catalyst composition is formed which may be used to catalyze the polymerization or oligomerization reaction.

The catalyst composition of the present invention may be used to catalyze the production of liquid polymers or oligomers of olefins of 2 to 6, or even 8, carbon atoms, as well as monophenyl or diphenyl derivatives thereof. By the terms polymerization and polymer it is meant to include herein copolymerization and copolymers as well as homopolymeri-zation and homopolymers, and oligomerization and oligomers, e.g. dimerization and dimers, trimerization and trimers, etc., as well as crossor co-oligomerization, e.g., crossor co-dimerization, etc. For example, by cross-dimerization, used here as being synonymous with co-dimerization, is meant the addition reaction combining one mole of a first olefin, for instance propylene. with one mole of a second olefin, for instance, butene, to form one mole of a cross-dimer, for instance heptene. By dimerization, on the other hand, is meant the addition reaction which simply combines two moles of a single olefin, for instance propylene, to form the respective dimer, for instance hexene. Polymerization and polymers are the terms here used to embrace all of these reactions and reaction products.

Thus, suitable feeds include, for instance, monoethylenically unsaturated olefins, preferably alphaolefins, such as ethylene, propylene and isobutene;

poly-ethylenically unsaturated olefins, preferably the dienes, such as butadiene-.l-, 3; and phenyl-substituted derivatives of the foregoing olefins, such as styrene,

' l,4-diphenylbutadiene-l,3 and l-phenylbutadienel,3.

The polymers produced by the action of the present catalyst composition will often be of 2 to about 4 monomer units per molecule, i.e., will often range from dimers to tetramers. The catalyst composition has been found, for example, to be especially suitable for the production of hexene fractions by the dimerization of propylene.

Polymerization can be effected by contacting the olefinically-unsaturated feed at a temperature-of about 10 to 300 F., preferably about 90 to 125 F., and at atmospheric, elevated or reduced pressures. Suitable. pressures include about 0 to 1,000 psig preferably about 300 to 600 psig. The amount of catalyst composition used in the reaction is that sufficient to effect polymerization of the feed and often is about 0.1 to l percent of catalyst composition (not including the solvent therefor) based on the weight of hydrocarbon feed.

The invention will be better understood by reference to the following examples.

EXAMPLE I A 300 cc. stainless steel autoclave equipped with an air driven magnetic stirrer was used as a reactor.'One m.mole (millimole) of cerous acetylacetonate, Ce(acac) and 3.7 m.moles of triphenyl phosphine, P, were charged simultaneously into the reactor with 40 ml. of chlorobenzene. While the reactorwas purged with nitrogen, these components were vigorously stirred at a temperature of -85 F. for about 20 minutes. The reactor was partially evacuated to introduce a chlorobenzene solution of ethylaluminum sesquichloride, Et Al Cl (28 m.moles) by suction through a syringe needle which was connected to a sampling valve. A small amount (5 ml.) of fresh chlorobenzene was drawn into the reactor to clear the residue of Et Al- Cl retained in the syringe needle. The total amount of chlorobenzene introduced into the reactor was g.

The reactor was tightly closed and the system was stirred for 5 minutes. Propylene was added into the reactor at less than 150 psig without heating the system. Liquid propylene, in the amount of 240 ml., was fed from a blow case to the reactor within 30 minutes. When addition of propylene was discontinued the system was allowed to react for an additional 60 minutes. In the course of reaction the pressure of the system continually dropped to 40 psig and the temperature was maintained in the range of to F. with the heat liberated by the reaction. Reaction was discontinued by discharging the light yellow reaction mixture into a cold flask through the syringe needle and quenching by the addition of dilute hydrochloric acid. The organic layer was isolated from a milky aqueous acid portion, dried over anhydrous sodium sulfate, and distilled into fractions. One hundred and three grams of propylene dimer product was recovered.

Thus, 103 g. of propylene was converted to product with 1 m.mol of catalyst solution (based on cerium content) within 90 minutes. Thistime period includes any induction period (possibly 20-30 minutes) which may have been required to form an active catalytic species. Total product was obtained in more than 85 percent yield. The structures of the products were identified by means of gas chromatography, mass spectroscopy, and

hydrogenation. Details of reaction conditions, catalyst EXAMPLE n soul 1.1 mimics. of 6am). and 4.8 m.moles of P were weighed into a reactor as in-Example I. Stirring was continued, for-3O minutes and then a chlorobenzene solution of 24 m.moles of Et Al Cl was added to the reactor. Propylene was then fed at 600 psig without heating the catalyst solution. About 60 minutes were required to feed 240 ml. of propylene. Soon after the addition of propylene was stopped, the pressure rapidly dropped to 200 psig and there was further bserved a very slow pressure drop during an additional 3% hours of stirring; At the final stage the pressure was 90 psig and the temperature was 95 F. In this run, 1 l4 plete the feeding of 200 ml. of propylene into the reactor. Seventy five grams of product was recovered in 74 percent yield. Product data is listed in Tables II and Ill.

' EXAMPLE v A binary catalyst system was prepared with l m.mol of Ce(acac) and 24 m.moles Et Al cl in chlorobenzene in the 300 cc. autoclave reactor. Introduction of propylene at 400 psig was started afterseveral minutes, and the temperature was maintained at l l0l F. throughout the reaction. The rate of propylene absorption was much lower than that observed, in the previous ternary catalyst solution. About 230' ml. of propylene was fed into'the reactor in 1 hour. The system was stirred for an additional 2 hours after'p'ropylene addition. The pressure dropped to a minimum of 280 psig phosphine,'remarkably affectedthecatalytic activity and yield of the product in the previous examples.-

lene dimeris essentially complete in less than 90' min-,

utes. In Tables I, II and Ill more details of the reaction and products are described.

EXAMPLE Ill Inanother run, 1.1 m.moles of Ce(acac) 4.8 m.moles of (1: 1, and 27 m.moles of Et Al Cl were charged into the reactor along with 75 g. of chlorobenzene solvent the samemanner as in the previous examples. Addition of propylene immediately followed the additionof the halide, and, unlike the procedure in Examples-I and Il, heating of the system was started at the same time. Since the exothermicity of the reaction raised -t he temperature of the system to 135 F., however, heating was discontinued. Soon after completion ofthe addition of 240 ml. of propylene at 600 psig over 40 minutes, .the pressure of the system very rapidly dropped to 250 psig within afew minutes. From this pressure it dropped very slowly to 50 psig during an additional 110 minutes. The organic portion (120 -g., excluding chlorobenzene solvent) was isolated from the aqueous portion, and by distillation l 17g. of the product was recovered. Therefore, 117 g. of propylene was converted with ,l.l m.moles Ce catalyst solution in 2% hours. The actual time-period required for the reaction of the designated amount of propylene appears to be inuch shorter than 2% hours.

EXAMPLE IV One m.moleof -Ce(acac) 4.8 m.moles of (MP, and 30 m.moles of EtgAlgClg were charged (along with 82 g. of chlorobenzene solution) into the reactor accordwithin 30 minutes after the addition of propylene was complete. Further pressure drop was negligibleover the next-1% hours. Propylene dimer, in the amount of 82 g., was recovered from the reaction mixture'Thus, only 82 g. of propylene was converted to product using 1 m.mole of Ce catalyst solution for 180 minutes.

This indicates that the. third component, triphenylarmpi /r A bright orange solution was prepared under nitrogen atmosphere in a glass bottle by mixing 0.5 m.moles of Ce(acac) and 5.5 m.moles of d P in 66 g. of chlorobenzene. A chlorobenzene solution of Et Al Cl was slowly injected into the orange solution with ice-water cooling. As soon as Et Al Cl was added, the color rapidly faded to yield a colorless clear solution. After the catalyst solution was removed from the ice-water bath, propylene was bubbled through the catalyst solution at atmospheric pressure and room temperature by means of a syringe needle. Vent gas from the reactor was condensed in a cold trap. Absorption andreaction of propylene were continuously observed by both elevation of liquid level in the catalyst solution and increase of condensatein the cold trap. An organic layer was isolated from an aqueous portion afer the reaction mixture was quenched with dilute I-ICI. Presence of hexene product in the organic portion was confirmed by gas chromatography. It was noted that even after the propylene had been bubbled through the solution for a few hours at room temperature, the catalyst was still stable and. active at that time.

EXAMPLE VII In another run, the catalyst solution was prepared with l m.mol otfCe(acac) 5.1 m.moles of (MP, and 32 m.moles of Et3Al2Cl3 in g. of chlorobenzene. Butene-l was introduced into the catalyst-solution, and the reaction was allowed to proceed at l20 F. and 500 psig for .4- hours. While the system was less active for this polymerization of butene-l than it was for propylene, the presence of octenes in the reaction mixture of this example wasv confirmed by means-of gas chromatography.

Catalyst Composition and Reaction Conditions Hydrogenation of Products Catalyst Composition, millimoles Reaction Conditions Example Ce(acac) 6,1 51 M 0 Chlorobenzene Pressure, Temp., Time,

No. (grams) psig F. min.

1 1.03 3.72 28 90' 180-40 85-75 90 11 1.10 4.80 24 90 600-90 87-100' 270 111 1.10 4.80 27 75 600- 115-120 150 IV 1.00 4.80 30 82. 100 87-115 150 V 1.0 24 80 400 120-110 180 V1. 0.58 5.50 25 66 0 -65 1 180 TABLE 11 Example No. I 1 11 111 IV Weight of Recovered Product, grams 103 1 14 1 17 Weight Yield oi Product, based on amount of propylene reactant. 92 94 74 Distribution of Product, wt. Fractions, wt. of total products:

C olefins 94.54 95.32 93.70 93.86 C olefins 0.78 0.09 0.71 1.12 I C olefins 4.67 4.60 5.59 5.13 Analyses by gas chromatography after hydrogenation or by mass spectrometer. Components, wt. of total products 4-methylpentene-l and 1.13 0.73 1.26 1.77 3-methy1pentene-l cis-4-rnethylpentene-2 4.40 3.55 4.55 7.19 2,3-dimethylbutene-l and 21.59 28.76 29.94 31.88 trans-4-methylpentene-2 hexene-l and 2-methylpentene-l 14.48 13.78 12.44 10.46

trans-hexenei 4.82 4.41 4.29 4.95 cis-hexene-3 0.38 0.91 0.62 0.58 trans-hexene-2 15.56 13.38 13.57 9.99 2-methylpentene-2 28.57 26.02 24.10 30.02 cis-hexene-Z and cis-3-mcthylpentene-2 2.98 3.55 3.61 3.17 2,3,3-trimethylbutene-1 0.88 0.52 C olefins 5.21 5.04 h 5.63

' Anulyrll by gas chromntngruphy.

T TABLE 111 Example No. Components in Hydrogenated Product, wt. 2,3-dimethylbutane Z-rnethylpentane n-Hexane C saturates EXAMPLE Vlll A catalyst solution, which was prepared with 1.0 m.mole of Ce(acac and 24 m.mol of Et Al Cl in 81 g. of chloroben zene solvent, was transferred into the reactor. Propylene was reacted with this phosphinefree catalyst solution for a period of 2.5 hours in the pressure range of about 280 to 420 psig and at about 1 10 to 122 F. 'The propylene was dimerized to hexenes at about 93 percent selectivity and 55 percent yield, based on the amount of propylene feed. Product distriubt ion obtained with this catalyst system is quite. similar to the results obtained with the catalyst systems} containing triphenylphosphine: catalyst activity, how-= ever, as indicated by the low product-yield, is substantially less in the phosphine-free composition.

Details of the reaction conditions and product analyses are listed in Tables lV, V and V1.

EXAMPLE 1X A similar catalyst solution was prepared by injecting chlorobenzene solution of Et Al Cl (22 m.moles) into a mixture of 0.7 m.mol of Ce(acac) and 26 m.moles ofdi P iii li IS rQBnZne. Total mm of 513355;

zene in this catalyst system was 85 g.

Immediately thereafter, the catalyst solution was introduced into the autoclave, ethylene was fed into the reactor at pressures in the range of about 60 to 150 psig v and at room temperature. A rapid pressure drop was observed along with temperature elevation within a few minutes. The temperature of the system was mainin Table IV. It appears, therefore, that under similarconditions ethylene is dimerized much faster than propylene in this catalyst solution.

EXAMPLE x Another ternary catalyst system was similarly prepared with 1.1 m.moles of LaCl '7l-l O, 5.2 m.moles of (p and 24 m.moles of Et Al C1 in g. of chlorobenzene. The system was not a homogeneous solution. Some precipitate, which may be attributed to the limited solubility of LaCl '1-1 O in chlorobenzene solvent, was observed to be suspended inthe system.

Propylene was introduced into the system at the pres- 5 sure range of about 300 to 500 psig and at about 120 F. The pressure drop pattern showed that reaction proceeded fairly rapidly under the aforementioned conditions. About 2- moles of propylene was dirnetized alsisting of trialkylaluminums, monoalkoxydialkylalu minums, dialkylaluminum hydrides, wherein the alkyl and alkoxy groups have up to about 6 carbon atoms; Grignard reagents; ally] tin complexes, alkyl tin complexes; and compounds represented by the formulas MAlR; and MBeR wherein M is an alkali metal and'R is alkyl of 2 to 6 carbon atoms, and

b. a Lewis acid selected from the group consisting most exclusively to hexene s in about percent con- 10 of aluminum chloride, zinc chloride, stannic version within 1% hours. The product distribution was chloride, boron trifluoride andboron trifluoride found to be as shown in Tables V and V1. etherates; and

TABLE IV Example No. Catalyst Composition, millimoles Reaction Conditions Ce(a'cac) 0 1 Et Al Cl Chlorobenzene Pressure, Temp, Time, (grams) psig F. min.

V111 1.0 0 24 81 280-420 110-122 150 [X 0.7 2.6 22 60-150 120-130 X 1.1 5.2 24 9S 300-500 90 Lea -711,0

T A l BLE V M Example No. V111 IX X weight it Yield of Product, based on amount of Olefin SS 60 reactant Distribution of Product, wt.

4-rnethy1pentene-l and 3-methylpentene-1 2.56 2.36 cis-4-methylpentene-2 7.29 9.16 2.3-dimethy1butene-l and trans-4-methylpentene-2 51.17 36.99 Hexene-i and Z-rnethylpentent-l 1.21 16.26 trans-hexene-3 4.72 4.14 cis-hexene 0.40 0.46 trans-hexene-Z 18.35 13.40 Z-methylpentene-Z 2.83 1332(1) cis-hexene-Z and cis-3-methylpentene-2 4.72 3.69 2,3,3-trimethy1butene-l 0 22(2) C, olefins 5.53 isobutene and butene-l 4.08

trans-butene-Z 66.47 cis-butene-Z 29.39

*' Anllylia by gas chromatography.

(l) 2-methylpentene-2 and 4,4-dimethylbutene-1. (2) 2,3-dimethyIbutene-2.

TABLE VI Example No. Components in Hydrogenated Products, wt.

2.3-dimethy1butane Z-methylpentane n-Hexane C saturates V111 0.94 63.27 29.62 5.67 x 75.29 22.71

It is claimed:

l. A catalyst consisting essentially of A. a lanthanide series metal compound selected from the group consisting of 2.5 non- 56mm Lewis acid reducing agent having the formula Or-ID U 55 wherein M is a metallic element of coordination numher it whose halides are Lewis acids, X is halogen having an atomic number of 9 to 53, .R' is hydrocarbyl of 2 to 6 carbon atoms, and y is a number having a value from greater than 0 to less than n;

C. a complex forming amount of a trihydrocarbyl phosphine,

the molar ratio of(B) to (A) being about 3 to 40:1, (8) being combined with (A) to reduce the lanthanide series metal (A) to a lower oxidation state'and the molar ratio of (C) to (A) being from about 1:1 to about 10:1

and components (A), (B) and (C) being combined to.

produce an effective oligomerization catalyst.

2. A catalyst of claim 1 wherein M is selected from the group consisting of aluminum, zinc and tin.

3. A catalyst of claim 2 wherein M is aluminum.

4. A catalyst of claim 1 wherein (B) is (B) (2) and X is selected from the group consisting of chloride ane bromide.

5. A catalyst of claim 4 wherein M is aluminum and X is chloride.

6. A catalyst of claim 4 wherein the molar ratio of (B) to (A) is from 5 to 30:1.

7. A catalyst of claim 5 wherein the molar ratio of (B) to (A from 5 to 30:1.

8. A catalyst of claim fwherein (C) is atiihydrocar byl phosphine of the formula Rllsp wherein R" is a hydrocarbon radical of 1 to about 12 carbon atoms.

9. A catalyst of claim 1 wherein (C) is a trihydrocarbyl phosphine of the formula Rllap wherein R is a hydrocarbon radical of 1 to about 12 carbon atoms.

10. A catalyst of claim 4 wherein (C) is a trihydrocarbyl phosphine of the formula Rllap wherein R" is a hydrocarbon radical of l to about 12 carbon atoms, and the molar ratio of (C) to (A) is from about 1 to 6:1.

1 l. A catalyst of claim 7 wherein (C) is a trihydrocar- .from the group consisting alkyl, aryl, alkaryl and aralkyl, and the lanthanide series metal is (A) (iii) and is selected from the group consisting of lanthanum and cerium.

14. A catalyst of claim 10 wherein each R" is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl, and the lanthanide series metal is (A) (iii) and is selected from the group consisting of lanthanum and cerium.

15. A catalyst of claim 11 wherein each R is selected fromthe group consisting of alkyl, aryl, alkaryl and aralkyl, and the lanthanide series metal is (A) (iii) and is selected from the group consisting of lanthanum and cerium. 

2. a non-protonic Lewis acid reducing agent having the formula R''(n y)M''Xy wherein M'' is a metallic element of coordination number n whose halides are Lewis acids, X is halogen having an atomic number of 9 to 53, R'' is hydrocarbyl of 2 to 6 carbon atoms, and y is a number having a value from greater than 0 to less than n; C. a complex forming amount of a trihydrocarbyl phosphine, the molar ratio of (B) to (A) being about 3 to 40:1, (B) being combined with (A) to reduce the lanthanide series metal (A) to a lower oxidation state and the molar ratio of (C) to (A) being from about 1:1 to about 10:1 and components (A), (B) and (C) being combined to produce an effective oligomerization catalyst.
 2. A catalyst of claim 1 wherein M'' is selected from the group consisting of aluminum, zinc and tin.
 3. A catalyst of claim 2 wherein M'' is aluminum.
 4. A catalyst of claim 1 wherein (B) is (B) (2) and X is selected from the group consisting of chloride and bromide.
 5. A catalyst of claim 4 wherein M'' is aluminum and X is chloride.
 6. A catalyst of claim 4 wherein the molar ratio of (B) to (A) is from 5 to 30:1.
 7. A catalyst of claim 5 wherein the molar ratio of (B) to (A) is from 5 to 30:1.
 8. A catalyst of claim 1 wherein (C) is a trihydrocarbyl phosphine of the formula R''''3P wherein R'''' is a hydrocarbon radical of 1 to about 12 carbon atoms.
 9. A catalyst of claim 1 wherein (C) is a trihydrocarbyl phosphine of the formula R''''3P wherein R'''' is a hydrocarbon radical of 1 to about 12 carbon atoms.
 10. A catalyst of claim 4 wherein (C) is a trihydrocarbyl phosphine of the formula R''''3P wherein R'''' is a hydrocarbon radical of 1 to about 12 carbon atoms, and the molar ratio of (C) to (A) is from about 1 to 6:1.
 11. A catalyst of claim 7 wherein (C) is a trihydrocarbyl phosphine of the formula R''''3P wherein R'''' is a hydrocarbon radical of 1 to about 12 carbon atoms, and the molar ratio of (C) to (A) is from about 1 to 6:1, the lanthanide series metal is (A) (iii) and is selected from the group consisting of lanthanum and cerium.
 12. A catalyst of claim 8 wherein each R'''' is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl, and (A) is selected from the group consisting of cerium and lanthanum.
 13. A catalyst of claim 9 wherein each R'''' is selected from the group consisting alkyl, aryl, alkaryl and aralkyl, and the lanthanide series metal is (A) (iii) and is selected from the group consisting of lanthanum and cerium.
 14. A catalyst of claim 10 wherein each R'''' is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl, and the lanthanide series metal is (A) (iii) and is selected from the group consisting of lanthanum and cerium.
 15. A catalyst of claim 11 wherein each R'''' is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl, and the lanthanide series metal is (A) (iii) and is selected from the group consisting of lanthanum and cerium. 